Process for controlling undesirable aldehyde and amine odors in treated textile material



United States Patent 3 196,036 PRESESS FOR CONTRbLLING UNDESIRABLE AL- DEHYDE AND AMINE ODQRS IN TREATED TEXTILE MATERIAL James F. Cotton, (lolumbus, Ga, and Sara L. Colqurtt, Lauett, Ala, assignors to West Point- Pepperell, Inc., a corporation of Georgia No Drawing. Filed Aug. 8, H60, Ser. No. 47,906 6 Claims. (Cl. 117-62) The present invention is concerned with a new type of treatment for avoiding or controlling the formation of the undesirable odors which are normally encountered in fabrics or similar materials treated with aldehyde resins, Water repellents and the like.

The principal object of the present invention is to provide certain novel improvements in the procedures described and claimed in US. Patents 2,870,041 and 2,928,758 and copending application Serial No. 817,083, filed June 1, 1959, the disclosure of the latter being incorporated herein by reference. This and other more specific objects will be apparent from the following detailed description of the invention.

According to the abovementioned US. Patents 2,870,- 041 and 2,928,758 and Serial No. 817,083, undesirable odors, such as aldehyde and amine odors, in fabric or other filamentary or sheet material treated with aldehyde resins and/ or water repellents containing quaternary ammonium compounds or amines, and normally subject to such odors as a result of said treatment, may be effectively controlled by treating the material with a compound supplying the HSO3 ion.

The procedures described and claimed in the above noted patents and Serial Nov 817,083 give satisfactory odor control whether the H80 ion is applied prior to curing of the resin or water repellent, or subsequent thereto. However, according to the present invention, it has been found that, with certain resin and water repellent treated fabric, the ease with which odor control is obtained may be greatly enhanced through the use of phosphates and/0r reducing sugars dissolved in a common bath with the compound supplying the HSO ion. This bath may also contain, if desired, other conventional treating agents which are used to obtain various effects on textiles and like materials, such as softeners, tints, bodying agents, etc. Additionally, the bath may include a volatile alkaline agent, e.g. aqueous ammonia, as described in US. Patent 2,928,758. It will be appreciated that the treatment with H80; ion and phosphate and/ or reducing sugar, according to the invention, may be effected simultaneously as a single operation with the resin and/ or water repellent application. As an alternative, the odor control operation may follow the resin and/ or water repellent treatment.

In practicing the procedures described in the abovementioned patents and Serial No. 817,083, it has been found that certain textile fabrics require more stringent application conditions than those which are normally required. For example, in certain cases, it may be necessary to have the bath containing the H50 ion at substantially higher temperatures and the dwell times in the bath usually must also be extended in order of obtain optimum control of aldehyde and amine odors. This presents a problem because the conditions of treatment on a commercial scale are usually keyed to the more difiicultly processable fabrics, since it is normally impracticable to separate the general run of fabrics into groups for processing under different sets of conditions. As a result, it has not always been possible to operate the odor control process using the HSO3 ion under optimum output conditions. However, with the incorporation of one or more phosphates and/ or reducing sugars, into the bath containing the H; ion as proposed herein, it has been found that reduced bath temperatures and dwell times in the bath are possible. Thus, less stringent conditions of operation may be imposed on the fabric, particularly those which have previously been difficult to process, with a reduction of dwell time in the treating bath and a resulting increase in output.

It has also been found that the use of one or more phosphates with resin treated fabric, in the manner proposed herein, offers the advantage that the resin is further stabilized so that the resin treated fabric is less subject to deterioration than comparable resin-treated fabrics which have been processed without phosphate in the odor control treatment. The exact reason for this unique result is not known although it appears that the phosphate retards or limits the degree of hydrolytic damage suffered by resins. It is not intended, however, that the invention should be limited to this theory or explanation.

Another adavntage of the use of a phosphate as defined herein is that this makes it possible to effectively buffer the fabric pH at certain chosen levels, the phosphate being appropriately elected to give the desired pH.

It is a surprising aspect of the invention that the use of one or more phosphates and/or sugar in conjunction with bisulfite, as proposed herein, substantially reduces the amount of bisulfite required to control aldehyde and amine odors. This is most apparent when the H80 application is carried out in conjunction with the application of resin to the fabric or like material. Without intending to limit the invention thereto, a possible explanation for this phenomenon is that, by one means or another, the phosphate and/ or reducing sugar prevent the reaction of the bisulfite with the odor producing bodies of the resin until after cure of the resin has been accomplished thereby reducing the. amount of bisulfite necessary for control of aldehyde and amine odors.

Still another unexpected advantage of the invention is the discovery that reducing sugars suppress the evolution of sulfur dioxide from bisulfite compounds. Thus, when the reducing sugar is incorporated into a treating bath embodying the H80 ion and the bisulfite concentration is in excess of that required for control of aldehyde and amine odors on the treated fabric, the reducing sugar reduces the evolution of sulfur dioxide from the bisulfite deposited on the fabric and prevents the odor of sulfur dioxide from becoming apparent. This is of especial interest in those cases in which the fabric may have been inadvertently treated with a large excess of bisulfite. By way of explanation only, and without intent to limit the present invention, it appears that the reducing sugar and bisulfite form a loose adduct which does not inhibit the control of aldehyde and amine odors from the resins and water repellents of the treated fabrics by the bisulfite ion but does slow the rate at which sulfur dioxide is evolved from bisulfite on the treated fabric after drying.

According to the present invention, any water soluble phosphate or reducing sugar which can be admixed with the compound supplying the HSO ion and is inert, i.e.

does not deleteriously afliect the fabric or other material being treated and does not react with the H80 compound and other auxiliary agents which may be included in the bath, may be used for the purposes described herein. The normal inorganic salts of: orthophosphoric acid (H PO such as disodium phosphate (Nag-IP pyrophosphoric acid (H P O such as tetra-sodium pyrophosphate (Na P O and polyphosphoric acids which contain the unit (HPO where n is 1 or greater, such as sodium tripolyphosphate, sodium hexametaphosphate and tetrasodium pyrophosphate are particularly of value because of low cost and availability. However, there may be used other inorganic and organic salts of the oxygen acids of phosphorous which are capable of being admixed in a common bath with the material supplying the H50 ion such as ammonium, alkali metal and alkaline earth metal salts as well as those of other metals which form suitable phosphates. Also suitable are salts formed in situ by the addition of free oxygen acids of phosphorous to solutions of salts such as sodium chloride and bases such as sodium hydroxide and those formed by the addition of phosphorous pentoxide, P 0 to solutions of salts and bases.

The amount of phosphate to be used in the treating bath can be varied but usually will fall within the range of at least 0.05% and up to about 4.0%, based on the total weight of the treating bath. Stated in another Way, the amount of phosphate may correspond from about 0.01 to 1.0 parts per part of H50; supplying compound. More than the indicated amount of phosphate can be used but no particular advantage appears to be gained thereby.

As the reducing sugar to be used in lieu of, or preferably in addition to, the phosphate according to the invention, there may be used any saccharide which in aqueous solution will reduce Fehlings or Benedicts solutions. Of particular value are the mono-saccharides as exemplified by glucose which is readily available at low cost. Other suitable mono-saccharides are: mannose, ribose galactose and fructose.

The amount of reducing sugar to be used will generally vary between a minimum of about 0.05% up to about 3% of the total bath weight or 0.01 to 1.0 parts per part of H50 supplying compound. Here again, more sugar can be used than indicated above if this should appear desirable in any particular case.

As in the process of US. Patent 2,870,041, any watersoluble organic or inorganic compound capable of forming the bisulfite ion in solution may be used as the odor controlling agent of the present invention. Particularly desirable is sodium meta bisulfite (Na S O because of its availability and low cost. However, there may also be used other water-soluble salts of sulfurous acid, for example, the sulfites and bisulfites of Group 1A of the periodic table, i.e. lithium, sodium, potassium, rubidium, and cesium, and of the alkaline earth metals of Group IIA, such as beryllium, magnesium, and calcium, as well as those of aluminum and Zinc. Ammonium sulfite and bisulfite, sulfurous acid per se or sulfur dioxide in solution may also be used. The amount of H50; supplying compound utilized herein can be varied but should not exceed the limits prescribed in the abovementioned patents and Serial No. 817,083. In fact, as noted heretofore, use of the phosphate and/ or reducing sugar makes it possible to reduce the amount of H30 compound necessary for odor control under prior practice. As a result, the amount of H50 compound used for odor control herein may only be 25 to 75% of the amount previously used under otherwise similar conditions. Treating temperatures may also be reduced by as much as to 60 C. and the dwell time may be reduced by as much as 50%.

7 It will be appreciated from the foregoing that the essential components of the impregnating solution used herein include the HSO supplying compound and the phosphate and/or reducing sugar. However, in addition to these components, the impregnating solution may also include other ingredients as indicated heretofore, such as, a volatile alkaline agent, e.g. ammonium hydroxide; and suitable wetting agents, e.g. Tergitol TMN (an alkyl ether of polyethylene glycol) or Wooncopen GW Reg. (a nonionic fatty amine complex). Other conventional finishing agents such as starches, fabric softeners, filling and bodying agents, lubricants, sewing assistants, dyes, tints and whitening and brightening agents may also be included in the impregnating solution. 7

For the purpose of determining whether the desired degree of odor control has been attained, the fabric, after treatment, with the HSOy supplying compound, may be steamed and the residual odor in the steam and hot fabric checked by smelling. (Two minutes steaming has been determined to be a practical test period.) Complete odor control is obtained when no formaldehyde or amine odor can be detected by this. method.

It has been indicated above that the phosphate used herein offers the further advantage of efiectively buffering the fabric or other treated material to maintain a desired pH. As will be understood by those in the art, buffers are materials which resist any change in pH Whether by addition of base or acid. The phosphates along with a number of other salts, acids and bases either alone or in combination fall in the general category of buffering agents or buffers. The salts of phosphoric acids are particularly good buffers. In the present invention, the combination of a phosphate such as tetra sodium pyrophosphate with the bisulfite appears to form a buffer which resists change in pH quite well. It has been found that, for the most part, when using tetra sodium pyrophosphate and sodium tripolyphosphate, the pH of th treated fabrics or other material falls in the narrow pH range of about 6.8 to 7.2 more or less.

Buffering of the fabric or other material within a narrow range around pH 7 appears to be important because this protects any resin in the material from damage by either bases or acids which might be liberated from the material on storage or which might be deposited on the material by various means. An excess of either base or acid will, of course, override the buffering capacity of the buffer. Fabric is also protected by the combination of phosphate and bisulfite proposed herein, from the effect known as alkali browning. This problem is especially apparent for white fabrics, particularly when they are finished on the alkaline side.

The invention is illustrated but not limited by the following examples wherein parts and percentages are by weight:

Example I An x 80 print cloth fabric which had been previously resin treated to yield 5% resin on the weight of the fabric using equal quantities of Aerotex UM and Aerotex M-3 (both of which are melamine-formaldehyde resins) was subjected to an after pad treatment to give 70% wet pickup using the following aqueous mixture:

Parts Sodium metabisulfitc 2 Alkylarylpolyethylene glycol (Deceresol NI Conc.) 0.2 28% aqueous ammonia 0.4

It was necessary to maintain the bath at the boil and to pass the fabric through the bath twice prior to drying at 300 F. for one minute in order to obtain odor control as evidenced bythe lack of odor exhibited by the fabric on steaming. However, when the steaming was continued over an extended period of time, some aldehyde odor became evident in the effluent steam indicating that the resin of the fabric might be suffering hydrolytic deterioration.

In a second bath, one part of tetrasodium pyrophosphate and 0.5 part of glucose replaced the aqueous ammonia. The bath temperature was lowered to 180 F. and the fabric was passed through once followed by drying as before. Complete odor control was obtained as evidenced by lack of odor exhibited by the fabric on steaming over an extended period of time, e.g. in excess of minutes. Thus, the use of tetra sodium pyrophos phate and glucose allowed a reduction of bath operating temperature, effectively reduced the dwell time of the fabric in the bath by 50% and effectively stabilized the resin of the fabric against hydrolytic deterioration. As an additional advantage, it was noted that the odor of the second bath was even less than that of the first.

Example II A woven fabric was treated with the following aqueous mixture at room temperature to achieve a 70% wet pickup:

Aerotex Resin 23 Special (a triazine-forrnaldehyde resin) 3.3 Catalyst UTX (an amine hydrochloride) 1.1 Sodium metabisulfite 3.0 Tetra sodium pyrophosphate 2.0 Glucose 0.5

The treated fabric was dried at 250 F for one minute and cured at 340 F., for one and one-half minutes. The fabric was free of aldehyde and amine odors under steaming even when the steaming was extended for a long period of time. When the phosphate and reducing sugar were omitted from a second bath, the quantity of sodium metabisulfite necessary for complete odor control had to be increased to 18 parts.

Example III A woven fabric resinated with a triazine aldehyde resin (i.e. Aerotex Resin 23 Special) and a durable water repellent including pyridine (namely Zelan AP) were passed through the first bath of Example I, the bath being maintained at the boil followed by drying one minute at 300 F. When tested for odor by steaming a slight amount of aldehyde and pyridine odor was present indicating that a longer dwell time inthe bath would be necessary for complete control of aldehyde and amine odors. When 0.5 part tetra sodium pyrophosphate was added to the bath, it was found that complete odor control was obtained on steaming even when the fabric was passed through the bath but once and the temperature of the bath was reduced to 180 F.

Example IV In the process of Example H approximately equimolar quantities of glucose and sodium metabisulfite in the ratio of 180 parts of glucose and 190 parts of sodium metabisulfite were combined in a water solution. A resin mix was prepared utilizing a sufficient quantity of the solution to contain approximately 5.0 parts of sodium metabisulfite to 8.3 parts of the triazine resin. The resin mix was applied to a cotton fabric, dried one minute at 250 F. and cured one and one-half minutes at 340 F. The fabric was free of aldehyde and amine odors under steaming.

The singular application of glucose in combination with sodium metabisulfite thus allowed a substantial reduction in the quantity of bisulfite necessary for complete odor control since, as in Example 11, 18 parts of sodium metabisulfite were required for odor control in the absence of the glucose.

Advantageously, the usual pungent odor of formaldehyde evident in formaldehyde resin padding mixes was completely removed.

Example V A rayon fabric was resinated with a urea-formaldehyde paste resin to contain 12% resin by weight. It was found that subsequent treatment with a solution containing 5.0 parts sodium metabisulfite, 1.0 parts aqueous ammonia, and 0.2 part Deceresol NI Concentrate as in Example I with a bath temperature maintained at the boil gave much improved odor characteristics to the fabric but there was still need for reduction in reagent concentration.

When 1.0 part sodium tripolyphosphate and 0.5 part glucose replaced the aqueous ammonia of the bath, it was possible to reduce the amount of sodium metabisulfite to 3.0 parts. The fabric treated in this second bath was free of aldehyde and amine odors even on steaming.

Example VI A non-woven fabric including a triazine-formaldehyde resin was padded twice through a bath consisting of 0.5 part sodium metabisulfite, 0.4 part aqueous ammonia and 0.1 part Wooncopen GW Regular (a nonionic fatty amine complex). The bath temperature was 180 F. This was followed by rinsing twice in water at F. and passing through a bath consisting of approximately 2.0 parts sodium metabisulfite, 1.8 parts aqueous ammonia, 2.0 parts of a 30% polyethylene emulsion and 0.2 part of Wooncopen GW Regular. The fabric was then dried. The fabric was found to be free of aldehyde and amine odors even on steaming, but there was a need for greater simplicity of operation.

The above process was replaced by passing the fabric twice through a bath consisting of 1.5 parts sodium metabisulfite, 0.75 part tetra sodium pyrophosphate, 0.25 part glucose, 0.2 part Deceresol NI, an alkylarylpolyethylene glycol, and 2.0 parts of a 30% polyethylene emulsion. The bath was maintained at 140 F. After drying, the fabric was tested for odor characteristics by steaming and was found to be free of aldehyde and amine odors.

Example VII A woven cotton fabric resinated with a triazine-formaldehyde resin and treated for water repellency with a water repellent based on a melamine-formaldehyde resin was passed through a bath maintained at P. which consisted of 1.5 parts sodium metabisulfite and 0.25 part tetra sodium pyrophosphate. The fabric was then dried two minutes at 300 F. Complete odor control was obtained as evidenced by lack of aldehyde or amine odors on steaming and water repellency of the fabric was excellent.

Example VIII A cotton print fabric was treated with a dye fixative based on melamine-formaldehyde resin to prevent bleeding of the print colors during subsequent processing. The fabric was subsequently resin finished with a combination of Aerotex UM and Aerotex M-S, both of which are melamine-aldehyde resins.

The fabric was passed through the following bath maintained at 180 F:

Sodium metabisulfite 2.0 Tetra sodium pyrophosphate 1.0 Glucose 0.5 Deceresol NI Cone. 0.2

The fabric was dried for one minute at 300 F., and found to be free of aldehyde and amine odors even on steannng.

Example IX The fabric of Example VIII was passed through the following solution maintained at 180 F:

Sodium metabisulfite 2.0 Sodium hexametaphosphate 0.5 Glucose 0.5 Deceresol NI'Conc. 0.2

The fabric was dried one minute at 300 F., and found to be free of aldehyde and amine odors even on steaming.

Example X A rayon flannel fabric resinated with a urea-formaldehyde resin was passed through the following solution maintained 'at 180 F:

Sodium metabisulfite 3.0 Glucose 0.5 Deceresol NI Conc. 0.2

Tetra sodium pyrophos'phateto pH 6.3.

The fabric was dried three and one-half minutes at 250 F. and was free of aldehyde and amine odors even on steaming."

Example XI A cotton fabric resinated with a melamine-aldehyde resin was passed through the following bath maintained at 180 F:

Sodium metabisulfite 3.0 Tetra sodium pyrophosphate 1.0

Deceresol NI Conc. 0.2

Example XII A 136 x 60 cotton broadcloth fabric resinated with a triazone resin (i.e. Permafresh LCR) was passed through the following bath maintained at 140 F:

Sodium metabisulfite 1.5 Tetra sodium pyrophosphate 0.5 Glucose 0.25 Deceresol NI Conc. 0.2

The treated fabric was dried for three and one-half I minutes at 250 F. The fabric was free of aldehyde and amine odors on steaming.

Example XIII A rayon challis interlining fabric with 15% ureaforrnaldehyde resin was passed through the following bath maintained at 180 F:

Sodium metabisulfite 4.0 Tetra sodium pyrophosphate 1.0 Glucose 0.5 Deceresol NI Conc. 0.2

The fabric was subsequently dried for three and onehalf minutes at 250 F. and was free of resin odors even on steaming.

Example XIV A cotton percale fabric resinated with Aerotex Resin 23 Special, a triazine resin, was padded through the following mix maintained. at 160 F:

Sodium metabisulfite 1.5 Glucose 0.5 Tetra sodium pyrophosphate 0.67 Deceresol NI Conc. 0.13

The treated fabric was dried one minute at 300 F. and was free of aldehyde and amine odors on steaming.

It will be appreciated that various modifications may be made in the procedures illustrated in'the above examples and the accompanying description without deviating from the scope of the invention. Thus, in lieu of textile woven or non-woven fabrics, other forms of fibrous materials such as textilefibers, yarns, paper, and films subject to odor problems may be treated in the manner described herein. These various forms of materials are broadly referred to in the appended claims as filamentary or sheet materials and the scope of the invention will be apparent from these claims wherein we claim:

1. In a process for controlling undesirable aldehyde and amine odors in filamentary andsheet material treated with a member of the group consisting of aldehyde resins, quaternary ammonium water repellents and amine water repellents, wherein said odor control process comprises impregnating said material with a compound supplying the ESQ; ion followed by drying in the presence of said ion toeffect said odor control, the improvement which comprises applying to the material along with said compound, a mixture of phosphate and reducing sugar.

2. In a process for controlling undesirable aldehyde and amine odors in filamentary and sheet material treated with a member of the group consisting of aldehyde resins, quaternary ammonium water repellents and amine water repellents, wherein said odor control process comprises impregnating said material with a compound supplying the HS03 ion followed by drying in the presence of said ion to effect said odor control, the improvement which comprises impregnating said material with an aqueous solution containing said compound, at least one phos phate and at least one reducing sugar.

3. In a process for controlling undesirable aldehyde and amine odors in filamentary and sheet material treated with a member of the group consisting of aldehyde resins, quaternary ammonium water repellents and amine water repellents, wherein said odor control process comprises impregnating said material with a compound supplying the H803 ion followed by drying in the presence of said ion to effect said odor control, the improvement which comprises applying glucose to the material along with said compound. 7

4. In a process for controlling undesirable aldehyde and amine odors in filamentary and sheet material treated with a member of the group consisting of aldehyde resins, quaternary ammonium water repellents and amine Water repellents, wherein said odor control process comprises impregnating said material with a compound supplying the HSO "--ion followed by drying in the presence of said ion to effect said odor control, the improvement which comprises applying a monosaccharide to the material along with said compound.

5. In a process for controlling undesirable aldehyde and amine odors in filamentary and sheet material treated with a member of the group consisting of aldehyde resins, quaternary ammonium water repellents and amine water repellents, wherein said odor control process comprises impregnating said material with a compound supplying the H ion followed by drying in the presence of said ion to effect said odor control, the improvement which comprises impregnating said material with an aqueous solution containing said compound and a reducing sugar, the amount of reducing sugar being from about 0.05% to about 3% of the total weight of said solution.

6. In a process for controlling undesirable aldehyde and amine odors in filamentary and sheet material treated with a member of the group consisting of aldehyde resins, quaternary ammonium water repellents and amine water repellents, wherein said odor control process comprises impregnating said material with a compound supplying the HSO ion followed by drying in the presence of said ion to eifect said odor control, the improvement which comprises applying to the material along with said compound, a reducing sugar that reduces a member of the group consisting of Fehlings solution and Benedicts solutions.

References Cited by the Examiner V UNITED STATES PATENTS 2,267,276 12/41 Hager 8116.3 2,870,041 1/59 Waddle 11762 2,928,758 3/60 Waddle 117-62 3,027,270 3/62 Cotton et al 117135.5 XR

WILLIAM D. MARTIN, Primary Examiner.

RICHARD D. NEVIUS, Examiner. 

1. IN A PROCESS FOR CONTROLLING UNDESIRABLE ALDEHYDE AND AMINE ODORS IN FILAMENTARY AND SHEET MATERIAL TREATED WITH A MEMBER OF THE GROUP CONSISTING OF ALDEHYDE RESINS, QUATERNARY AMMONIUM WATER REPELLENTS AND AMINE WATER REPELLENTS, WHEREIN SAID ODOR CONTROL PROCESS COMPRISES IMPREGNATING SAID MATERIAL WITH A COMPOUND SUPPLYING THE HSO3- ION FOLLOWED BY DRYING IN THE PRESENCE OF SAID ION TO EFFECT SAID ODOR CONTROL, THE IMPROVEMENT WHICH COMPRISES APPLYING TO THE MATERIAL ALONG WITH SAID COMPOUND, A MIXTURE OF PHOSPHATE AND REDUCING SUGAR. 